Process for production of acrylates from epoxides
The methods of the present invention comprise the steps of: providing a feedstock stream comprising an epoxide and carbon monoxide; contacting the feedstock stream with a metal carbonyl in a first reaction zone to effect conversion of at least a portion of the provided epoxide to a beta lactone; directing the effluent from the first reaction zone to a second reaction zone where the beta lactone is subjected to conditions that convert it to a compound selected from the group consisting of: an alpha beta unsaturated acid, an alpha beta unsaturated ester, an alpha beta unsaturated amide, and an optionally substituted polypropiolactone polymer; and isolating a final product comprising the alpha-beta unsaturated carboxylic acid, the alpha-beta unsaturated ester, the alpha-beta unsaturated amide or the polypropiolactone.
1. A method for the synthesis of acrylic acid comprising the steps of:
providing a gaseous feedstock stream comprising ethylene oxide and carbon monoxide;
directing the feedstock stream to a first reaction zone where it is contacted with a metal carbonyl compound and where at least a portion of the ethylene oxide is converted to a carbonylation product stream comprising beta propiolactone;
directing the carbonylation product stream to a second reaction zone where it is contacted with a catalyst, which catalyzes the conversion of beta propiolactone to acrylic acid, wherein the conversion of beta propiolactone to acrylic acid is performed in a continuous flow format;
withdrawing an acrylic acid product stream from the second reaction zone; and
isolating acrylic acid from the product stream.
2. The method of claim 1 , further comprising the step of adding water to the carbonylation product stream before it enters the second reaction zone.
3. The method of claim 1 , wherein the conversion of ethylene oxide to beta propiolactone is a gas phase reaction.
4. The method of claim 1 , wherein the metal carbonyl compound has a formula [QM y (CO) w ] x , where:
Q is any ligand or more than one ligand and need not be present;
M is a metal atom;
y is an integer from 1 to 6 inclusive;
w is a number such as to provide the stable metal carbonyl; and
x is an integer from −3 to +3 inclusive.
5. The method of claim 1 , wherein the metal carbonyl compound comprises an anionic metal carbonyl.
6. The method of claim 5 , wherein the anionic metal carbonyl compound comprises a moiety selected from the group consisting of: [Co(CO) 4 ] − , [Ti(CO) 6 ] 2− , [V(CO) 6 ] − , [Rh(CO) 4 ] − , [Fe(CO) 4 ] 2− , [Ru(CO) 4 ] 2− , [Os(CO) 4 ] 2− , [Cr 2 (CO) 10 ] 2− , [Fe 2 (CO) 8 ] 2− , [Tc(CO) 5 ] − , [Re(CO) 5 ] − , and [Mn(CO) 5 ] − .
7. The method of claim 5 , wherein the anionic metal carbonyl compound comprises [Co(CO) 4 ] − .
8. The method of claim 5 , wherein the anionic metal carbonyl compound comprises [Rh(CO) 4 ] − .
9. The method of claim 1 , wherein the metal carbonyl compound comprises a neutral metal carbonyl compound.
10. The method of claim 9 , wherein the neutral metal carbonyl compound is selected from the group consisting of: Ti(CO) 7 ; V 2 (CO) 12 ; Cr(CO) 6 ; Mo(CO) 6 ; W(CO) 6 Mn 2 (CO) 10 , Tc 2 (CO) 10 , Re 2 (CO) 10 Fe(CO) 5 , Ru(CO) 5 Os(CO) 5 Ru 3 (CO) 12 , Os 3 (CO) 12 Fe 3 (CO) 12 Fe 2 (CO) 9 Co 4 (CO) 12 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Ir 4 (CO) 12 , Co 2 (CO) 8 , and Ni(CO) 4 .
11. The method of claim 9 , wherein the neutral metal carbonyl compound comprises Co 2 (CO) 8 .
12. The method of claim 1 , wherein the metal carbonyl compound comprises a solid.
13. The method of claim 1 , wherein the metal carbonyl compound is supported on a solid.
14. The method of claim 13 , wherein the solid support is selected from the group consisting of inorganic solids and polymer supports.
15. The method of claim 13 , wherein the solid support is selected from the group consisting of: silica, glass, alumina, zirconia, diatomaceous earth, metal oxides, metal salts, ceramics, clays, molecular sieves, kieselgur, and titanium dioxide.
16. The method of claim 13 , herein the solid support is selected from the group consisting of silica gel, alumina, and glass.
17. The method of claim 1 , wherein the ratio of carbon monoxide to ethylene oxide in the feedstock stream is between about 1:1 and about 100:1.
18. The method of claim 1 , wherein the ratio of carbon monoxide to ethylene oxide in the feedstock stream is greater than about 10:1.
19. The method of claim 1 , wherein the feedstock stream is provided to the first reaction zone at a pressure between about 20 and about 200 atmospheres.
20. The method of claim 1 , wherein the feedstock stream is provided to the first reaction zone at a temperature between about 50 and about 200° C.
21. The method of claim 1 , where the catalyst in the second reaction zone comprises an acid.
22. The method of claim 21 , wherein the acid comprises phosphoric acid.
23. The method of claim 21 , wherein the acid comprises a solid acid catalyst.
24. The method of claim 1 , wherein the carbonylation product stream is provided to the second reaction zone as a gaseous stream.
25. The method of claim 24 , wherein the carbonylation product stream comprises a mixture of beta propiolactone and carbon monoxide.
26. The method of claim 24 , wherein the carbonylation product stream is essentially free of unreacted ethylene oxide.
27. The method of claim 1 , wherein the step of isolating the acrylic acid comprises condensing the acrylic acid.
28. The method of claim 1 , further comprising the step of oxidizing ethylene gas to provide the ethylene oxide feedstock stream.
29. The method of claim 28 , wherein the step of oxidizing ethylene gas comprises contacting ethylene with oxygen in an ethylene oxidation reactor in the presence of a suitable catalyst to convert at least a portion of the ethylene to ethylene oxide, withdrawing a gaseous ethylene oxide stream from the ethylene oxidation reactor; and combining the gaseous ethylene oxide stream with carbon monoxide to provide the feedstock stream.
30. A method for the synthesis of acrylate esters comprising the steps of:
providing a gaseous feedstock stream comprising ethylene oxide and carbon monoxide;
directing the feedstock stream to a first reaction zone where it is contacted with a metal carbonyl compound and where at least a portion of the ethylene oxide is converted to a carbonylation product stream comprising beta propiolactone;
adding a C 1-8 alcohol to the carbonylation product stream comprising beta propiolactone;
directing the carbonylation product stream comprising beta propiolactone and the C 1-8 alcohol to a second reaction zone where it is contacted with a catalyst which catalyzes the conversion of beta propiolactone and the C 1-8 alcohol to the corresponding acrylic acid ester, wherein the conversion to acrylic acid ester is performed in a continuous flow format;
withdrawing an acrylic acid ester product stream from the second reaction zone; and
isolating an acrylate ester from the acrylic acid ester product stream.
31. The method of claim 30 , wherein the C 1-8 alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, hexanol, and 2-ethyl hexanol.
32. The method of claim 30 , wherein the C 1-8 alcohol comprises methanol.
33. The method of claim 30 , wherein the C 1-8 alcohol comprises butanol.
34. The method of claim 30 , wherein the metal carbonyl compound comprises a solid.
35. The method of claim 30 , wherein the metal carbonyl compound is supported on a solid.
36. The method of claim 30 , wherein the solid support is selected from the group consisting of inorganic solids and polymer supports.
37. The method of claim 30 , wherein the solid support is selected from the group consisting of: silica, glass, alumina, zirconia, diatomaceous earth, metal oxides, metal salts, ceramics, clays, molecular sieves, kieselgur, and titanium dioxide.
38. A method for the synthesis of acrylic acid comprising the steps of:
providing an ethylene stream;
contacting the ethylene stream with oxygen in the presence of a catalyst to provide an ethylene oxide stream;
adding carbon monoxide to the ethylene oxide stream to provide a feedstock stream;
directing the feedstock stream to a first reaction zone where it is contacted with a metal carbonyl compound and where at least a portion of the ethylene oxide is converted to a carbonylation product stream comprising beta propiolactone;
directing the carbonylation product stream to a second reaction zone where it is contacted with a catalyst, which catalyzes the conversion of beta propiolactone to acrylic acid, wherein the conversion of beta propiolactone to acrylic acid is performed in a continuous flow format;
withdrawing an acrylic acid product stream from the second reaction zone; and
isolating acrylic acid from the product stream.
39. The method of claim 38 , wherein the ethylene oxide remains substantially in the gas phase between the oxidation step and the first reaction zone.